Process of treating petroleum



Feb. 13, 1923. 1,445,040. L. c. READ.

PROCESS 0F TREATING PETROLEUM.

FILED APR. 4, I917.

- lnwntor Patented Feb. 13, 1923.

UNITED STATES PATENT OFFICE.

LANDON CABELL READ, OF LOS ANGELES, QCALIFORNIA; CLARA GENEVIEVE READADMINISTRATRIX OF SAID L. CABELL READ, DECEASED.

PROCESS OF TREATING PETROLEUM.

Application filed April 4,

T 0 all whom it may concern: I

Be it known that I, LANDON CABELL READ,

a citizen of the United States, residing at,

. of producing only hydrocarbons other than those in the originalsubstances.

As applied to petroleum or other hydrocarbons this invention moreparticularly relates to processes for treating hydrocarbons wherebyproducts are formed which do not exist in the original substance; thatis, in contradistinction to merely separating different constituents ofan original substance, this process is, in this specific case, one inwhich hydrocarbons of a character different from the original areproduced. However, it will of course be understood that my process doesnot preclude the possibility of preliminarily extracting the desirableconstltuents from the original substances; as it is not. an object toeffect changes or transformation in all of the hydrocarbon constituentsbut only in those which maybe changed or transformed into more desirablesubstances.

. Thus I mav first separate the lighter and more desirable constituentsby any ordinary separation means before proceeding to trans form theremaining constituents into more desirable substances.

It may be stated as a primary object of this invention to transformoriginal hydrocarbons so as to produce the largest possible quantity ofthe most valuable product at the least cost; and for this purpose Iprovide a system of operation inwhich the control conditions may bevaried to produce a maximum yieldof various desirable roducts andminimum. yields of undesirab e products; a system in which, the controlof quantity and quality may be said to be separate and independent ofeach other so that each may be controlled for maximum results; and a1917.- Serial N0. 159,705.

system of control in which the deposition of free carbon may beprevented as far as posslble, if not eliminated entirely.

In accomplishing my objects I operate upon the hydrocarbons in thatstate which allows of the greatest possible independent variation ofcontrol of the controlling factors of the reaction-in the vapor state.This state of the hydrocarbons not only allows me to lndepen ently varythe factors of control such as temperature and pressure, but allows meto obtain reactions which are pecullar to the gaseous state alone. Asother controlling means, I may here mention the use of superheated waterva or, to be partially disassociated for suppiying hydrogen tohydrocarbons and oxygen to the carbon whlch may be thrown out; the useof air, oxygen, carbon-dioxide or a mixture of any or all'of these withor without steam for the supply of oxygen to the carbon which may bethrown out. The carbon dioxide may be either pure or'mixed with othergases as in the products of combustion of various fuels. Such gases,either reactive or inert, may be used to vary the control factor ofconcentration, as hereinafter explained.

The action of superheated steam in my process includes (1) a physicaleffect in preventing overheating of the hydrocarbon gases, (2) acatalytic effect in accelerating the reaction taking place shorteningthe time of subjection of the vapors to high temperature, 3) a chemicalaction of oxidation of any free carbon thrown out of the hydrocarbons,(4) a liberation of hydrogen corresponding to the oxygen used by thecarbon to form raw material for hydrogenating the unsaturatedhydrocarbons; (5) variation in the mass action relationship; and (6) adiluting effect for reduction of the partial pressures of thehydrocarbons.- It may be well here to note that although the instantpercentage of disassociation of the water va-,

por or carbondioxid at the temperatures used may be comparatively small,yet the using up of the decomposition products tends to produce furtherdecomposition to restore equilibrium conditions; resulting in acontinuous supply of the decomposition products in a comparatively largefinal amount.

Generally speaking, equilibrium conditions in a reaction system-thefactors which control reaction, include the factors of time,

there is, as a matter of actualfact, very lit- I tle chance that anyone'selected set of control factors will produce the optimum conditions.This is particularly true as ap lied to petroleum hydrocarbons. It is ano ect of my invention to provide a system wherein all four of thesecontrol factors may be controlled and varied independently each of theother, so that proper conditions may be imposed for the maximum(production ofthe most highly desirable. pro ucts.

It is my conception that the largest production of the most desirableand valuable product is not to beobtained by a s ngle operatiton or bythe 1mpos1t1on of a single set of control co-nditionsupon the originalhydrocarbons; that some at least, of the most desired products, are notproduced d1- rectly from the original hydrocarbons, but fromintermediate products; that the most highly desired products may be, tosome extent at least, products which are made under different kinds ofconditions in difi'erent chains or processes of reaction from those inwhich the intermediate products are made. The intermediate products areproduced in greatest quantity and value by conditions which usually are,and as a matter of fact in'a great many" cases are, the very opposite ofthe best conditions for the production of the valuable final products.Consequently, in order to obtain maximum efficiency, in order to obtainmaximum recovery of the highest quality, I operate in more than onestage of operation; typically, a stage or stages in which controlconditions are held for maximum production of inter mediate products,and a setting, or fixing, of those intermediate products by a stoppingof the reactions which would carry them on into undesirable products,and then a stage or stages in which the conditions are made best fortransformation, conversion, etc., of the intermediate products to thefinal products desired. This statement may not be entirely or strictlytrue, as some minorreactions which are not desired may go on in any ofthe stages, and as there may be in any circumstance, certain-originalsubstances, they are not transformed into the final products mostdesired.

But, speaking in a general way, I provide in my process a system ofoperation in which the control of one thing is not dependent upon thecontrol of another thing; in which the variation of one control factoris not interfered with by variation in another control factor; and inwhich control to produce a certain desired intermediate or final resultis not' interfered with by the necessity of control to producesome'other result; and in which the original substances are takenthrough a series of ste s in which the control conditions are inepend'ently manipulated, so that, once the desirable product isobtained, it is so to speak, set and held while another desired productis produced, or the course of reaction is changed for the purpose ofproducing a further desired product.

In setting or fixing the intermediate prod- ,uct I may of courseaccomplish the desired result by changing any one of the controlfactors, these being independently variable.

For instance, after'breaking down complex petroleum carbon at hightemperature under vacuum, I may then apply pressure while still keepinga moderately high temperature. The original complex open chainhydrocarbons will not be reproduced because the conditions necessary fortheir reproductiton are not made. This operation I give merely as anillustration of whatmay be done to change the course of reaction or tofixor set the intermediate products, 'to keep them from from going on intheir previous reaction, or on the other hand, to keep them fromreverting back to their original state, even in the case of suchreactions as may be reversible.

v I conceive that it is impracticable to impose all of the conditionshereinbefore stated at any one time or in a single stage, or in a singlereaction space. My conception,therefore, is that only by working-in aplurality of stages, where the difi'erent control con- -d1tions,hereinabove illustrated, can be successively applied, can the maximumresults be had. Conditions for maximum results at each of the stages maybe more or less nearly approximated by calculation in advance, byreference to known reaction procedures, and generally by formerexperience.

With this general idea of my system of procedure in mind, I now proceedto the explanation of typical and actual processes and the resultsthereof. I illustrate with processes of only two stages; but the methodence.

In an actual process a small boiler 10 has been used for generatingsteam, provided with a coil 11 for super-heating the steam to atemperature of from (500 to 800 F. The oil to be treated is led inthrough a pipe l2 from any suitable source of supply and injected withthe superheated steam into the upper end of a double coil of pipe 13 ina furnace 14. The apparatus at 15 may be in the formof any ordinaryinjector, for draw ing in and injecting oil, and for atomizing and thusfacilitating the vaporizing of the oil at the point of injection. Theoil is thus fed into the coil 13, with the-steam, practically in theform of vapor. An air compressor 20 draws the vapors from the coil 13and compresses them to any desired de gree; at the same time keeping thedesired pressure, either greater or less than atmospheric pressure, butpreferably less, upon the coil 13. A gage is provided at 21 for notingthe pressure in the coil 13; and a control valve at 22, in conjunctionwith those at 22 and 22, provides the means for regulating the pressureby regulating the suction action of the compressor 20 upon the coil 13.From the compressor the vapors are compressed into a condenser coil 25wherein the desired pressure is maintained, under control of thedischarge valve or valves 26 and 26 a gage being provided forobservation of the pressure. At 28 I provide a separat; ing chamber fromwhich the fixed gases may escape through the pipe 29 and from which theliquids may escape through a suitable trap outlet 30.. The gas outletpipe 29 may be provided with a discharge control valve 26 and the liquidoutlet 30 may have a discharge control valve 26; and the pressuremaintained in the condenser coil and in the separating chamber may becontrolled with one or both of these valves. For instance, the liquidmay be discharged intermittently, but the valve 26 may be set todischarge the gases at such a rate as to hold the proper pressure uponthe condenser coil and the separating chamber. I prefer to hold pressureupon the separating chamber as well as upon the condenser coil, ratherthan on the condenser coil alone, for the reason that the gases are thennot permitted to expand in the presence of the condensates andconsequently do not absorb and carry off so much of the liquids as theywould do if allowed to expand in their pres- The time elements andpressures in the various parts of the system are regulable andcontrollable by the general design, capacity, etc. of the apparatus tosuit it in the first place to some particular relation of the factors ofcapacity, pressure, time of passage of vapors, etc.; and then, in anyconstructed and organized apparatus, by the speed of operation of thecompressor, and by the manipulation of the various valves.

The compressor may be operated to keep the desired pressure, preferablyless than atmospheric, on the furnace coil, for the purpose of obtainingfirst those products which a low pressure would induce; ahd the outletvalve 26 or 20 on the condenser coil is then regulated to cause thedesired pressure to be built up in the condenser coil.

In the particular cases, hereinafter described, the original gasolenecontents of the oil had been removed by othermeans; and this willnormally be done before the oils are subjected to my process, becausethere is nothing to be gained by subjecting the original, valuable anddesirable contents of the oil to my process. The fact that the firststep of my process takes place under partial vacuum facilitates thecombination of my apparatus directly with a distilling apparatus, asshown in the drawing. I illustrate a still at 40 from which the vaporsare drawn off through pipe 12 into the pipe 13 leading to coil 13. Theline 13 conducts the resultant from the coil 13 to the compressor 20 anda pressure relief valve at 13 may be used to protect the apparatusagainst rise in pressure. The arrangement may otherwise be similar tothat previously described; the only operating difference being that inusing the still the oils are delivered in initially gaseous state to theheating coil 13. Vith this general combination of apparatus it ispractical to first distill off the lighter desirable products from anoriginal petroleum and then take off the heavier vapors to be treatedaccording to my process. However, the general results are the same ineither case herein described. It will of course be understood that thestill may be of any form in which oil vapor may be generated either withor without admixtures of superheated steam, and the remaining steamneeded may be mixed at the apparatus 15, as before.

As particular instances of my method of procedure, I now describespecific operations. In one particular case the initial oil used Was a26 gravity fuel distillate from California oil. The furnace temperaturewas estimated to be about 2000 F. The temperature in the heating coil isdesigned to be sufiicient to cause oxidation of carbon by oxygen fromdissociated Water vapor, and to cause hydrogenation of the hydrocarbonsby the liberated hydrogen; this temperature being also 'suflicient tocause the rapid break down of the high boiling hydrocarbons to lowboiling hydrocarbons at the reduced pressure. The time period duringwhich the vapors were subjected to the heat in coil 13 is sufficient toallow this. break down to proceed to the desired extent; and furtherbreak down is then arrested by the immediate cooling of the gases whenthey pass through the pipe 13 to the compressor. In a small unit nospecial cooling means is necessary for this reduction of temperature. Avacuum of15" was maintained upon-the furnace coil. The pressure in thecondenser coil was. in this case, atmospheric. The recovery wasapproximately 80% of the origioily products being separated, distilledand analyzed. it was found that 64% of the products was lightdistillates of boiling points between 132 and 320 F.; while 36% wasnaphthalene oils of boiling points 300 F to 406 F. and anthracene oilsof boiling points 500 to 597 -F. and a. small amount of pitch and loss.In other words, treated in this particular manner (and it is not claimedthat these particular conditions are the most efiicient for producingthe proclucts finally evolved), approximately 51% of the originalsubstance was recovered as light distillates of a quality useful asgasolene.

The foregoing described operation is one of a number carried on in theapparatus illustrated, in which different operations a number ofdifferent c0ntr0l' conditions were imposed. For instance, the followingdescribed operation illustrates results obtained by imposing conditionsdifferent from those imposed above. In this case, the oil was a 48gravity engine distillate from a California oil and the total recoverywas approximately 80% of the original. The temperature in the furnacecoil was estimated to be approximately 1700to 2000 F. and a vacuum of 12was maintained in the furnace coil. These control conditions weresomewhat similar to those maintained be-,

fore; but a pressure of 100 pounds per square inc-h was maintained inthe condenser coil. The quality of the recovered products is shown bythe following tabu-. lated results of distillation:

Distillation.

Quantity taken, 300 CC.; 100%.

Total If)? It will be noted that the temperatures in 'in the originalsubstance; but the substantial difference was between the final con,-

denser pressures. I find from a number of runs, and from varying thefinal condenser pressure, that a pressure between approx1- mately eightyand one hundred twenty five pounds per square inch (varying withdifferent circumstances) is sufficient and desirable to cause theproducts obtained in the last described run. Examination of the 64% oflight oils from the first described operation has shown that theycontained a very large percentage of unsaturated hydrocarbons; whileexamination of the 47% of light oils from the second described operationindicated a content of from one-third to one-half of toluene, theremainder being principally saturated, with only a sliuht quantity ofunsaturated hydrocarbons. Jxami'nation of the recovered oily products,of both the above described operations, showed the presence of easilyseparated pyridene bases and terpenoid hydrocarbons to a greater or lessextent, whilst the recovered aqueous products showed the presence ofalhedydic and other oxygenated hydrocarbon products to a small extent.

There was some difference.

In each of the above described specific I cases the weight of watervapor used was approximately one-half the weight of hydrocarbons. Thisamount of water vapor is not only sufficient for the purposes herein setforth, of oxidation, hydrogenation, catalytic action, etc., and for thepurpose of influencing the'mass action by varying the concentration onaccount of its reactivity; but also for further variation of the massaction by influencing the concentration by virtue of its dilutingeffect. For varying the concentration and causing dilution.independently of the pressures and temperatures used, I' may introduceatotally inert fluid, as hereinbefore stated. The timeelements in eachof the above described specific cases were uniformly very short. It issomewhat diflicult to state exactly what the time elements were, due toconditions of varying volumes, etc.; but it may be generally stated thatthe total time element from beginning to end of these processes wasapproximately five seconds, divided as follows: Approximately threeseconds for subjection to the high temperature under low pressure,approximately one second for falling of temperature before compression,and approximately one second for compression and condensation. In bothcases the temperature to which the vapors fell before compression, or atwhich they were compressed, did not exceed approximately 1200 F. In somecases it may be well to keep the gases, after compression, at theirtemperature of compression for a slight interval before cooling andphysical condensation. so as to allow suflicient time forthe chemicalreactions of condensation, etc. to be practically completed before thevapors are cooled below a temperature at which such reactions can goforward at suitable speed. However, I have. found that such necessaryper-10d 1s, in fact. comparatively short. The final temperature at thed15- charge of the condenser was practically atmospheric. regardless ofthe pressure there maintained.

The above described specific operations are typical of others which havebeen carried out; all with the substantial result of obtainance of acomparatively large percentage of low boiling hydrocarbons; uniformly apercentage very much in excess of any percentage obtained by any knowncracking system or system of distillation. And it will be seen how thesespecific in stances conform to the general statement of procedure I havehereinbefore made; how I first apply one set of controllable conditions.and then another, to the whole body, varying the conditions to suitcircumstances and to suit the nature of the desired final products.

Considering the large number of combinations possible under such extremeflexibility of so many control conditions, it is quite impossible tostate the final result for each particular combination. (Alnd I mighthere add that I have so far only been able to try a few of the-m.) Butit is sufiicient to say in abroad way that, with primary temper aturesaround 1300 I. and at about atmosphere primary, and 1 atmosphere final,pressure the final product will contain considerable olefins,acetylenes, etc., and some benzene and other cyclic hydrocarbons; withtemperatures up to 2300 and at about 7} atmosphere primary, and 10atmospheres final, pressure, the o-lefines and acetylenes, etc., areconsiderably diminished and the benzenes and other cyclic hydrocarbonsconsiderably increased. The distillation fraction of any of theseproducts corresponding in boiling points with commercial gasolene can beused with advantage in place of that article; it is, moreover, anexcellent solvent and can be worked up profitably for its large contentof benzene, toluene and other valuable cyclic hydrocarbons, the contentof any one of which cyclic hydrocarbons can be increased or diminishedby special variations of control conditions to suit the particular casein hand.

It should be understood that I do not limit myself to the introductionof steam or other oxygen bearing vapors or'gases, or inert gases, whichmay be introduced either for the purpose of reacting with the freecarbon or of forming addition or substitu-' tion products of thehydrocarbons themselves or for varying the concentration of the reactingsubstances, or for the mere purpose of dilutling the reacting system.For instance, any of the halogens, say, chlorine, may be used forreacting with the carbon and for obtaining different results alongsimilar lines; and other gases, vapors or liquids either with or withoutsteam, or other oxygen bearing gases, may be used to bring aboutspecific effects due to their composition. I claim my invention is broadenough in scope to include any and all such applications of. it. I

\Vhile the theoretical basis of the explanations may not be fullycorrect, I have given them as my explanation of what actually occurs inmy process, and in order to render my process fully intelligible in itsworkings and my invention fully intelligible in its scope. It will beobvious that the described operations, steps and applications ofcontrolling factors may be applied to hydrocarbons, etc., and insituations, other 90 than herein specifically stated, and with variousforms of apparatus; in fact, that many variations may be made Within thegeneral scope and extent of my invention. I do not conceive of myinvention as limited to any of the specific procedures herein stated,but rather to include those general procedures of which these particularprocedures are specific instances. Accordingly I have not given theabove descriptions in a limiting 100 sense, but in a sense typifying andindicating the invention and I do not limit myself to the specificprocedures, etc., herein set forth excepting as particularized in thefollowing claims. These claims are intended 105 to cover briefly andconcisely the whole subject matter of my invention, generically andspecifically, and whatever modifications, variations, etc., may liebetween the most general and most specific claims.

Having described a preferred form of my invention, I claim:

1. The process of chemically converting hydrocarbons that embodies firstsubjecting them to a cracking temperature at a low 115 pressure to causechemical conversion, then subjecting the resultant gases and vapors toreduction of temperature and to an increase of pressure to cause furtherchemical conversion. i

2. A process of chemically converting hydro-carbons, embodying firstsubjecting an original body of hydrocarbons to control conditionsincluding a temperature of approximately 2000 F. and a pressure less 125than atmospheric to cause chemical conversion, and then subjectingsubstantially the whole of the converted products to an increase inpressure to cause chemical conver= slon.

. hydro-carbons,

chemically converting hydro-carbons, embodying first subjecting anoriginal body of hydro-carbons to control conditions includin atemperature of approximately 2000 and a pressure less than atmosphericto cause chemical conversion, fora certain time period in the presenceof water vapor, and then subjecting the whole body of resultant vaporsto an increase in pressure to cause further chemical conversion. 4. A.process of chemically converting hydro-carbons, embodying firstsubjecting them to relatively high temperature and to pressuresubstantially not more than atmospheric to cause chemical conversion,then subjecting the whole of theresultant gases and vapors to reductionof temperature and then to an increase of pressure to cause furtherchemical conversion and condensing the product.

5. A process .of

3. A process of chemically converting embodying first subjecting themsubstantially exclusively in 'vapor phase to relatively high temperatureand to pressure substantially not more than atmospheric to causechemical conversion, then subjecting the'resultantproducts to anincrease in pressure to cause chemical conversion.

6. A' process of chemically converting hydro-carbons, embodying firstsubjecting them to relatively high temperature and to pressuresubstantially not more than atmospheric to cause chemical conversion,then subjecting the resultant products to a.

diminution of temperature and an increase in pressure to cause chemicalconversion.

7. The herein described process of treating hydrocarbons, embodyingfirst subjecting them substantially exclusively in vapor phase to arelatively high temperature at a low pressure in admixture with reactiveand hydro-carbons and then v the presence of an inert gases whereby thecontrolling factors of temperature and pressure and concentration may bemaintained independently of each other, to effect chemical change insuch cooling the admixture ofvapors and subjecting the whole of thesameto an increase in pressure, to effect further chemical densing theproduct.

8. The herein' described process of treating hydrocarbons, embodyingsubjecting them to relatively highheat and pressure substantially notmore than atmospheric in excess of water vapor, said water vapor beingin excess of the amount required to supply hydrogen and oxygen, forreaction with the hydrocarbons and the e cessacting as an inert diluentby which the concentration of the hydrocarbon may be controlledindependent of the pres-- sure. r

9. The herein described process of treat,

. taining these change and coning hydrocarbons,

embodying subjecting them in vapor phase substantially exclusively torelatively high temperature at a pressurev substantially not more thanatgases being in excess of the amount re quired for reaction with thehydrocarbons and the excess acting as a controllable diluent by whichthe concentration of the hydrocarbons may be controlled independent ofthe pressure.

11. The herein described process of chemically converting hydrocarbons,embodying first subjecting an original body of the same to relativelyhigh temperature and relatively low pressure and concentration andmainconditions each independent of each others by carrying on suchsubjection with the hydrocarbons,

cooling and condensing the resulting prod-.

ucts while under pressure,

12;. The herein described process of chemically converting hydrocarbons,first subjecting an original body of the same to relatively hightemperature and relatively low pressure and concentration andmaintaining those conditions each independent of each of the others bycarrying on such subjection with the hydrocarbons substantiallyexclusively in the vapor phase and in admixture with water vapor inexcess of the amount of water vapor that will react with thehydrocarbons at the temperature employed, the excess being controllablein amount and thus forming a controllable diluent to vary and controlthe concentration; and then somewhat cooling the resulting products andsubjecting them to in creased pressure while still at a temperatureconsiderably above atmospheric, and then cooling andcondensing theresulting products while under pressure.

13. The herein described process of chemically converting hydrocarbons,embodying first subjecting them-in the presence of water vap r to'atemperature sufiiciently high to substantially ex-' clusivelyin thevapor phase and. in ad- "mixture with a diluent controllable inembodying cause partial dissociationof the water vapor and oxidation of.carbon with the oxygen thus freed, under a pressure substantially notmore than atmospheric,'then subjecting the whole of theresultant gasesand vapors to increase of pressure, and condensing the product.

14. The herein described process of chemically converting hydrocarbons,embodying first subjecting an original body of hydrocarbons to controlconditions including a relatively high temperature and a pressuresubstantially not more than atmospheric to cause chemical conversion,then subjecting substantially the Whole of the converted products to adiminution of temperature but still maintaining the temperature above atmospheric and to an increase of pressure while at that diminished hightemperature, then to reduction of temperature to approximatelyatmospheric; and then finally'relieving the pressure to atmosphericpressure.

15. The herein described process of chemically converting hydrocarbons,embodying firstsubjecting them substantially exclusively in vapor phaseto a relatively'high temperature at a pressure substantially not morethan atmosphericin admixture with reactive and inert gases, whereby thecontrolling factors of temperature and pressure and concentrationmay bemaintained independently of each other, then subjecting the resultantvapors to a, diminished high temperature without material change 1npressure, then to an increase in pressure, then to decrease in pressureto approximately atmospheric pressure.

16.-A procem of treating hydrocarbons,

embodying subjecting them to a relatively high temperature insubstantially exclusive vapor phase and in the presence of water vaporand under apressure substantially not more than atmospheric,then-reducing the temperature but still maintaining itabove normalatmospheric temperature and materially increasing the pressure, and thencooling the vapor while under increased pressure, and finally relievingthe pressure.

17. A process of treating hydrocarbons,

' embodying first subjecting them to relatively high temperature andpressure substantially not more than atmospheric in the presence of anexcess of Water vapor, said Water vapor being in excess of the amountrequired to supply hydrogen and oxygen for reactionwith the hydrocarbonsand the excess acting as-an inert diluent by which the concentration ofthe hydrocarbons may be controlled independent of the pressure, and thensubjecting the products to an increase of pressure. y In witness that'Iclaim the foregoing I have hereunto subscribed my name this 29th day ofMarch, 1917.

4 o LICABELL READ. Witnesses:

Enwoon H, BARKELEW,

JAMES T. BARKELEW.

